27
Soap, Fatty Acids, and
Synthetic Detergents
Janine Chupa,* Steve Misner* and
George A. Smith**
SOAP AND FATTY ACIDS
Introduction
The origin of the word "soap" is traced to sac-
rificial Mount Sapo of ancient Roman legend.
The mixture of fat and wood ashes that
reacted to form soap was carried by rain to the
banks of the Tiber River and was found as a
clay deposit useful for cleaning clothes. 1
The boiling of fats with ashes was recorded
as early as 2500 B.c. Commercial soap-making
was a widespread art in the Middle Ages in
Europe. The invention of the soda ash process
by LeBlanc in 1791, and the discovery by
Chevreul in 1811 that soap was composed of a
mixture of fatty acids paved the way to mod-
em soap-manufacturing processess. 1•2
Chemistry
The modem definition of soap relates to
cleansing agents derived from fats, oils, and
other fatty derivatives: the soaps are alkali
*Colgate Palmolive Company, Piscataway, NJ-Soap
and Fatty Acids.
**Huntsman Corporation, Austin, TX-Synthetic
Detergents.
1098
and ammonium salts of fatty acids containing
from 8 to 22 carbon atoms. These fatty acids
are generally a mixture of saturated, unsatu-
rated, and polyunsaturated moieties:
CH3(CH2 ) 10COOM: saturated soap
CH3(CH2) 6CH 2CH =CHCHiCH2 ) 6COOM:
mono-unsaturated soap
CH3 (CH2MCH2 CH =CH) 2CHiCH2) 6COOM:
di-unsaturated soap
CHiCH2CH =CH)3CHiCH2) 6COOM:
poly-unsaturated soap
[M = Na, K, (HOCH2CH 2) 3NH+]
In general, two types of chemical reactions
are utilized in the manufacture of soap: the
saponification of triglycerides (fats and oils)
and the neutralization of fatty acids (which
themselves are produced from the triglyc-
erides by a variety of methods, most notably
splitting or hydrolysis of fats and oils with
steam under high pressure). Sodium hydrox-
ide (the predominant alkali employed in the
manufacture of soaps), potassium hydroxide,
sodium carbonate, and triethanolamine are
s
Riegel Handbook of Industrial Chemistry, I Oth Edition
Edited by Kent. Kluwer Academic/Plenum Publishers, New York 2003
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1099

Saponification
3 RCOONa + Glycerin
(NaOH) Neutral !'at
(Soap) saponification
Process

RCO-OCH 2
RCO-OCH
RCO-OCH 2
Triglyceride
Fat
Splitting
3 RCOOH + Glycerin

l
Fatty Acid

Neutralization
(NaOH)

3 RCOONa l'atty Acid

Neutralization
(Soap) Process
Fig. 27 .1. The chemistry of soap manufacture.

Methanol
Triglyceride --------------~~ RCOOMe + Glycerin
Catalyst
Fatty Methyl Ester

l Saponification
(NaOH)
RCOONa + MeOH
(Soap)
Fig. 27 .2. Fatty methyl ester process for soap manufacture.

the most commonly utilized alkaline moieties
in these processes (Fig. 27.1). 3' 4
In recent years, soap manufacture by an
alternate route, the saponification of fatty
methyl esters, has been under development,
most notably in Japan (Lion Corporation)
and Italy (Ballestra). The fatty methyl esters
are obtained from the methanolysis of
triglycerides; inorganic alkali, quaternary
ammonium salts, and enzymes (lipase)
have been used as catalysts for methanol-
ysis in commercially practiced processes
(Fig. 27.2). The methyl ester process for soap
manufacture is typically more capital and
cost intensive vs. the more traditional
fats/oils saponification and fatty acid neutral-
ization processes.
Manufacturing Technology
Several designs of commercial equipment,
based on the two processes described in
Fig. 27.1, are available for the manufacture
of soap.
1100 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

Fatty Acid is more commonly practiced in many other

Neutral Fat Saponification Neutralization parts of the world, especially in Asia. More
Kettle Processes Mazzoni SC and SCC recent trends in lauric oil pricing have driven
Semi-boiled Alfa Laval the purchase and use of palm kernel oil and
Boiled Sato palm kernel olein as cost-effective alterna-
Modern Processes tives to coconut oil in the West. The frequent
Mazzoni SCNC-N, SCNV-N Dial Saponiflex substitution of coconut oil with palm kernel
Binacchi CSWE, BV oil is done primarily for cost optimization of
Alfa Laval Centipure
Hitachi
soap-manufacturing feedstocks. Among other
Dial Saponiflex triglycerides, cottonseed oil, ricebran oil, cas-
tor oil, neem oil, sunflowerseed oil, fish oil,
A critical review of these processes is beyond and olive oil have also been used as indige-
the scope of this chapter. However, the nous feedstocks in many developing nations.
processes themselves are described in a sub- The use of palm stearin, the by-product of
sequent section. palm oil fractionation, is increasing in use
as a substitute for tallow outside of tallow-
producing markets. Depressed pricing
Raw Materials
in 2000 and the recent fears of Bovine
The triglycerides (triesters of fatty acids with Spongiform Encephalopathy (BSE) or Mad
glycerin) are the basic raw materials for the Cow disease have driven this use trend in
manufacture of soap utilizing a variety of Europe. Fatty acid composition and analytical
processes. These triglycerides, as a renewable characterization data of some of the key fats
resource, occur widely throughout the plant and oils utilized for soap production are given
and animal kingdoms. in Table 27.1.
Soap products in the United States are pro- Most of the fats and oils utilized for soap
duced almost exclusively from tallow (beef) manufacture require a combination of steps:
fat and coconut oil or their fatty acid deriva- degumming, deodorization, refining, and
tives. The utilization of palm oils, palm kernel bleaching, which are further discussed in the
oil, and their derivatives for soap manufacture section on fatty acids.

TABLE 27.1 Fatty Acid Distribution and Analytical Characterization of Soap

Base Fatty Acids
Fatty Acid Distribution Coconut Stripped Coconut Palm Kernel Palm Tallow
Caprylic (C 8H 160 2) 7 1 4
Capric (C 10H200 2) 6 1 5
Lauric (CizllzPz) 48 55 50
Myristic (C 14H28 0 2) 19 22 15 2 2.5
Palmitic (C 16H3z02) 9 11 7 42 27
Stearic (C 18H360 2) 2 2 2 5 20
Oleic (C 18H3p 2) 8 7 15 41 42
Linoleic (C 18H 3z02) 1 1 1 10 5
Linoleic (C 18H300 2 1
C2JC 22 isomers 2.5
Characterization Data:
Titer, C 26 29 25 40 40
Iodine value (IV) 10 5 18 55 55
Color, Gardner, max. 5 1 5
Acid value (AV) 270 255 205
Saponification value (SV) 270 255 205
Color, Lovibond, 5-~" 10Y/1R 4.5Y
0.6R
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
For both saponification and neutralization
reactions, sodium hydroxide is the most com-
monly used base. In some special situations,
such as the manufacture of transparent and
translucent soaps, potassium hydroxide and
triethanolamine are also employed.
Functional Properties of Soap
Almost as a rule, the solubility of soap in
water increases with an increase in the size of
the monovalent cation (base); however, an
increase in the size of a divalent cation (Mg +2,
ca+ 2) results in a decrease in the solubility. An
increase in the chain length of the fatty acid
moiety of soap results in a decrease in the sol-
ubility of soap, whereas the presence ofunsat-
uration results in an increase in its solubility.
In general, an increase in the water solubility
is accompanied by an increase in the softness
and use-up properties of soap. Adequate solu-
bility results in good performance in soft
water, although in hard water, lather decreases
due to the formation of insoluble ca+ 2 and
Mg+ 2 salts. Cleansing bars formulated with
various levels of synthetic detergents (com-
bars or syndets) provide improved perform-
ance in hard water conditions.
Consumer-acceptable lather requires the con-
sideration of a variety of lathering attributes,
such as the speed with which lather is gener-
ated, volume, quality (i.e., loose or creamy),
and the stability of the lather. In general, the use
of fatty acids of C 10--C 12 chain length provides
a voluminous, lacey foam while fatty acids of
longer chain length, from c16 to c18' contribute
to a richer, creamier foam.
Thus, a combination of coconut (C 10--C 12)
and tallow (C 16-C 18) fatty acids is most suit-
able from the viewpoint of providing a bal-
ance in lathering attributes to deliver
consumer-acceptable lather. Commonly
accepted ratios of these soap feedstocks are
80-85 percent tallow and 15-20 percent
coconut oil for standard purpose bars and
60-70 percent tallow, 30-40 percent coconut
oil for the higher lathering bar-soap products.
Cleansing bars formulated with free fatty
acids (superfatting) improves the quickness of
lather generation and provides an open, bub-
bly foam. Commonly accepted levels of
1101
superfatting range from 1-7 percent for vari-
ous types of bar soaps. Various methods are
employed to evaluate bar lather attributes. 5
Manufacturing Processes
The following describes neutral fat saponifi-
cation and fatty acid neutralization, the two
principal processes used for manufacture of
soap in the world markets today.
Neutral Fat Saponification. In the saponifi-
cation of triglycerides with an alkali, the two
reactants are rather immiscible. Because
saponification is a bimolecular nucleophilic
substitution (SN2), the kinetic rate enhance-
ment is achievable by both a high-shear mixing
and an increase in the reaction temperature
during the processing. Increasing the pressure
of the reaction assures that vaporization does
not occur at the high reaction temperatures and
helps to accelerate conversion of the fatty feed-
stocks and of alkali to soap as well. The saponi-
fication reaction is self-catalyzed to some
extent: the formation of soap product affects
the emulsification of the two immiscible reac-
tants, causing an acceleration of the reaction
rate by providing increased surface area for the
saponification reaction to occur.
The amount of alkali required to saponify a
triglyceride blend is calculated by the follow-
ing equations:
Triglyceride + 3NaOH
~ 3ROONa+Glycerin
NaOH = weight oil X [SV X 0.000713]
X 100/NaOH(%) in solution
=weight oil X SV(1 g/1000 mg)
(MW NaOH/MW KOH)
(100%/%NaOH) (27-1)
where SV =saponification value (mg KOHl
g triglyceride) and MW = molecular weight.
In general, the most commonly used soap
feedstocks have these saponification values:
(g NaOH/100 g Triglyceride)
Beef tallow 14.09
Coconut oil 18.32
Palm kernel oil 17.81
Palm oil 14.19
Palm stearin 14.26
1102 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
The use of these values simplifies the calcula-
tion of the stoichiometric alkali equivalent,
for example:
100 g beef tallow X 14.09 g NaOH/
100 g tallow X I g 50% NaOH caustic/0.5 g NaOH
= 28.2 g 50% NaOH caustic required
The process of a typical triglyceride saponi-
fication plant is given as a flow diagram in
Fig. 27.3. 6 Feed streams to the plant are the
fats/oils, caustic, brine, and water both to
convert the triglycerides to soap and to pro-
vide the necessary processing environment.
The two distinct product streams of saponifi-
cation are wet, or neat soap and spent lye that
contains the bulk of the by-product glycerin
from this reaction. The essential components
of this plant include proportioning pumps
(mass flow meters are replacing proportion-
ing pumps for reasons of reduced mainte-
nance, higher accuracy, and reliability) for
introducing correct quantities of reaction
components into a reactor autoclave, which
operates at temperature and pressure condi-
tions appropriate for a rapid and complete
reaction. The saponification mixture is recir-
culated within the autoclave. Since the tem-
perature of the saponified soap/lye mixture is
elevated, effective separation is made possible
by passing this mass through a cooler and
then to a static separator for separation of the
unwashed soap from the spent lye solution.
The soap, then, is contacted with washing lye
countercurrently in an extraction column to
separate glycerin (as spent lye) from the soap
mass. Centrifugal separators remove
entrained lye from the soap directly after
extraction. This centrifuging step reduces
moisture and electrolyte content from the
soap that is required in downstream process-
ing stages. Excess alkalinity in the neat soap
(60-63% total fatty matter) is neutralized, or
trimmed with lauric oil (coconut or palm ker-
nel typically). This finished base soap is dried
(typically on vacuum spray-type dryers) to
produce soap as pellets (78-82% total fatty
matter), ready for processing into finished
product on finishing lines (Fig. 27.4).
Soap Drying. The soap mass obtained after
the completion of saponification (neat soap) is
most commonly dried nowadays on vacuum
spray dryers. The moisture content of soap is
thus reduced from 30-35 percent in neat soap
to 8-18 percent in soap pellets (soap flakes or
chips are produced on APV-type dryers, after
milling). A variety of vacuum spray-dryers,
from single-stage to multi-stage designs, are
available from several manufacturers. The
operation of a single-stage vacuum spray-dryer
involves the pumping of neat soap at 80-85°C
through a shell-and-tube heat exchanger where
the soap is heated by high-pressure (6-10 bar)
steam passing through the outside tube in a
countercurrent manner. The soap is preheated
to 135-155°C and sprayed onto the walls of a
cylindrical vacuum chamber through a revolv-
ing nozzle. The thin layer of dried and partially
cooled soap deposited on the walls of the vac-
uum chamber is removed by rotating scrapers
and falls to the bottom of the chamber onto a dis-
charge plodder. This plodder extrudes the dried
soap mass in the form of noodles or pellets.
The excess moisture is flashed under
45-60 mm Hg vacuum and removed as vapor
after scrubbing to recover any soap fines
carried-over with the exiting vapor stream.
Proper control of moisture, temperature, vac-
uum, flow rate, nozzle pressure, and scraper
function ensure the drying of acceptable qual-
ity soap pellets. Typically these soap pellets
are conveyed pneumatically to storage
bins/silos that act as surge for the soap finish-
ing process. Soap storage silos are con-
structed of stainless steel and have angled
bottoms that direct soap pellets toward cen-
trally located twin discharge screw conveyers
for efficient transfer to the finishing lines.
Fatty Acid Neutralization. The acid-base
reaction of fatty acids with alkali to produce
soap (below) is much faster than the corre-
sponding reaction of triglycerides with alkalis.
RCOOH + NaOH ~ RCOONa + ~0
(27-2)
The amount of alkali (NaOH) required to neu-
tralize a fatty acid blend can be calculated as
follows:
NaOH =[weight fatty acid
X 40]/[MW fatty acid] (27-3)
0888
uuuuuuuu STRAINERS en
0
)>
:a
SPENT LYE .,
F lft-1: ~
.....
<
)>
~
c
!'l
)>
2
c
en
<
2
WAtfl! .....
::1:
m
.....
n
cm
. .. . . .....
m
DOSING GROUP AEAClOII FHDPUW FEED FEED PUMP TURBODISPERSER ::11:1
COOLING"""' IRANSFER
G)
PUMP """'
m
2
Fig. 27 .3. Continuous neutral fat oil saponification plant. (Courtesy G. Mazzoni S.p.A., Busto Arsizio, Italy) .....
en
....
....
Cl
w
 ....
....
Cl
.j:o.

2":!
m
C)
m
W.4TER r.:
(I)
::1:
)>
2
c
m
0
0
""0
"TI

2
c
c:
(I)
-1
::1:1
,....
>
(")
SECOND ::1:
STACiE HEAT m
RllST EXCHANCiEfl ~
STACiE HEAT
EXCHANCiEfl Cii
-1
::1:1
<
VENT

Fig. 27.4. Two-stage toilet-soap spray dryer. (Courtesy G. Mazzoni S.p.A., Busto Arsizio, Italy)
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
or NaOH = weight of fatty acid X AV
X 0.000713
where AV =acid value (mg KOH/g of fatty
acid), and the remaining portion of the equa-
tion being derived as in (27-1).
The average molecular weight of a fatty
acid blend is calculated from the following
equation:
MW fatty acid
= 56.1 X 1000/AV
= (MW KOH/AV) X (1000 mg/g)
X (1 mole KOH/1 mole fatty acid)
The average molecular weight of a fatty
acid blend is calculated from the following
equation:
MW fatty acid= 56.1 X 1000/AV (27-4)
where AV (acid value of fatty acid
blend)= mg of KOH required to neutralize
1 g of fatty acid.
A typical Mazzoni fatty acid neutralization
soap plant is illustrated in Fig. 27.5. 6 The
operation of this plant involves the pumping
of the reactants through preheaters to a tur-
bodisperser, or high-shear mixer, where the
contact of the reactants with each other initi-
ates the formation of neat soap. The soap
mass, which is partially reacted at this stage,
then proceeds to the mixer where it is recircu-
lated until the neutralization is complete. The
completion of the neutralization reaction is
monitored continuously by an electric poten-
tial (millivolt, mV) measurement for alkalin-
ity. The neat soap is then dried by vacuum
spray-dryers, as described earlier, to produce
soap pellets ready for finishing into soap bars.
Soap Finishing. The starting point for soap
finishing is usually the amalgamator, a hori-
zontal mixer that coarsely blends soap pellets
with minor ingredients such as color and fra-
grance. The soap mix from amalgamation is
conveyed to subsequent processing stages like
milling and refining to provide satisfactory
homogenization and working of the soap
before extrusion. A mixer/refiner process is
also available for blending of soap pellets with
minor ingredients on a more continuous basis.
1105
Sufficient working of the soap through fme-
mesh screens in the refining stages provides
uniformity and frictional heat necessary to
produce acceptable-quality billets for pressing
into bars. The finished product is extruded
from the last plodder as a continuous slug.
Vacuum is provided at the final extrusion
chamber to evacuate entrained air. This step
ensures the extrusion of a uniform slug that
will not separate or exhibit surface bubbles/
deformities. A multi-blade chain cutter or uni-
blade cutter with blades separates the extruded
slug into individual "billets" that are stamped
with a press into soap bars of the desired size
and shape.
The wrapping, cartoning, and end packag-
ing machinery complete the bar finishing
lines. The schematic diagrams of a variety of
soap finishing configurations are illustrated
in Fig. 27.6.
Fatty Acids
The fatty acids are produced industrially from
triglycerides. This process involves the steps
shown in Fig. 27.7. 7a,b
Refining involves the purification of triglyc-
eride to remove impurities (phosphatides,
polyethylene, chlorophyll, heavy metals, off-
odors, color bodies) by a combination of
acid/alkali washing, clay/activated silica bleach-
ing, deodorization, and hydrogenation steps.
Splitting, or the hydrolysis of triglycerides
is usually performed with high-pressure
steam, resulting in the formation of split
crude fatty acids and glycerin. The production
of fatty acids by more sophisticated "split-
ting" processes, such as hydrolysis of fatty
methyl esters, ozonolysis of unsaturated fatty
acids, and chemical oxidation is practiced in
special situations.
Distillation of split fatty acids results in the
improvement of chemical, color, and odor
quality of the finished product.
Fractionation and Physical Separation
Distilled fatty acid streams are separated to
obtain individual components of those fatty
acid streams in a higher state of chemical
purity. Fractionation is performed to separate
FATTY CAUSTIC SODA
ACIDS BRINE SODA ASH

HOLDING
MIXER

CARBON
DIOXIDE
PREHEAlER SEPARATOR

HOTWAlER
GENERATOR

TO SOAP
DRYING
PLANT
FIRST TRANSFER
DOSING GROUP TURBODISPERSER PUMP
Fig. 27 .5. Continuous fatty acid neutralization plant. (Courtesy G. Mazzoni S.p.A., Busto Arsizio, Italy)
 DUPLEX VACUUM CUTTER SLUG PRESS
AMALGAMATOR SIMPLEX
REFINER PLODDER EJECTOR

Vl
0
l>
.:0
.,
~
-1
<
l>
~
c
Vl
DUPLEX VACUUM CUTTER SLUG PRESS
AMALGAMATOR DUPLEX REFINER l>
PLODDER EJECTOR 2
c
Vl
<
2
-1
:I:
m
:::!
(")

c
m
-1
m
:a
C)
m
2
DUPLEX VACUUM CUTTER SLUG PRESS -1
AMALGAMATOR SIMPLEX ROLL MILL Vl
REFINER PLODDER EJECTOR
........
Fig. 27.6. Toilet-soap finishing line. (Courtesy G. Mazzoni S.p.A., Busto Arsizio, Italy) Q
.....
 1108 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
Triglyceride
~·
Refining
Splitting
Distillation
'if
Fractionation
Distillation to separate
lower molecular weight
(C-6 to C-14) fatty acids
Example:
Coco fatty acid .. C-8 (Capric acid)
C-10 (Caproic acid)
C-12 (Lauric acid)
C-14 (Myristic acid}
Fig. 27.7. Production of fatty acids from triglycerides.
the more volatile lower molecular weight fatty
acids (C 8--C 14 chain length). Physical separa-
tion is practiced to obtain higher molecular
weight, less volatile, or thermally unstable
fatty acids (C 16--C 18 chain length).
Hydrogenation is utilized to reduce the
unsaturation and poly-unsaturation of fatty
acids. Hydrogenated fatty acids can also be
produced by the hydrogenation of triglyc-
erides followed by splitting of the resulting
fat/oil blend. The selective reduction of di-
and poly-unsaturation is accomplished fre-
quently by the use of nickel-based specialized
catalysts in a process often called "touch"
hydrogenation.
In the partial hydrogenation of the
unsaturated moities the isomerization of the
double bonds of mono-unsaturated compo-
nents is a common occurrence; it results in the
Washing, Bleaching, Deodorizing, Hydrogenation
Hydrolysis to produce split fatty acids and glycerin
Purification of split fatty acids
'V
Separation
Physical separation
of higher molecular weight
(C-16 to C-18) fatty acids
Example:
Tallow fatty acid-+ Stearic acid
Oleic acid
transformation of the cis to the corresponding
trans stereoisomer. As the physical properties
of these isomers may vary significantly, their
impact on the properties of the final product
should be evaluated rather carefully, for little
information is available on this subject at
present.
Fat Refining
A typical fat refining plant (Alfa-Laval
process) for the acid washing of fats and oils
is illustrated in Fig. 27 .8.8 The triglyceride is
degummed to remove phosphatides and other
impurities like mucilage, proteinaceous
matter, and trace metals by acid washing with
citric or phosphoric acids, and then is sent to
a bleaching plant where it is dehydrated and
treated with an activated clay for the removal
 ACID CONDITIONED WATER AGG..OMERATION
OIL TANK

ACID PHOSPHORIC
MIXER ACIO TANK
C/l
0
l>
.:0
.,
~
.....
ACID DEGUMMED <
OR BLEACHED OIL l>
_...., ~
c
~
GU.lS
l>
FEED FEED ECONO- FEED f'H)SI"!-iffiiC SEPARATOR DEGUMMING GUM TRANSFER 2
HEATER ACID FU.f' FEED PUMP SEPARATOR PUMP PUMP c
STRAIJIER f'I.M' MIZER C/l
BLEACHED
<
- (Jj[
2
.....
:I:
m
:::!
(")
Fig. 27 .8. Acid degumming plant for acid washing offats and oils. (Courtesy A/fa-Laval, Tumba, Sweden)
cm
.....
m
:D
C)
m
2
.....
C/l
......
0
tD
1110 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
of color bodies, heavy metals, chlorophyll,
and polyethylene (Fig. 27.9). 6
Fat Splitting Processes
The direct reaction of triglycerides with alkali
followed by acidification or the treatment of
triglyceride with water (with or without an
acid catalyst) results in the splitting of
fats/oils into fatty acids and glycerin. The
splitting, or hydrolysis of fats/oils with water
can also be performed by using various lipase
enzymes as catalysts. The enzyme process is
still in the developmental stages. The inter-
esterification of triglycerides with methanol
followed by acid or alkali cleavage of the
resulting fatty methyl ester is used for the pro-
duction of certain molecular weight (C 8--C 10)
fatty acids; those methyl esters are generally
the by-products of fatty alcohol production
(Fig. 27.10).
The splitting of fats/oils can be done
either in a batch (Twitchell process) or in a
continuous (Colgate-Emery process) mode;
the enzyme-based processes are still under
development for commercial applications.
A comparison of these processes follows. 9a,b
Hydrolysis Conversion
Process Time (hr) ("/o)
Twitchell batch 8-24 95
Continuous 1-3 98-99
Enzyme 72 98
The manufacture of fatty acids from triglyc-
erides via their reaction with alkali followed
by acidification is not used commercially.
However, the recovery of fatty acids from
alkali refining of fats/oils (to produce acid
soaps) and soap reboiling operations (the
recovery of fatty acids from the acidification
of soap waste streams) are practiced still in
special situations, for example, in edible oils
refining where soapstock that is generated
from chemical (alkali) refining requires
acidulation to produce acid oils with commer-
cial value.
Industrially, the fatty acids are pro-
duced predominantly by the high-pressure,
high-temperature splitting of triglycerides.
Both batch and continuous processes are
available, the continuous process being in
greater worldwide use today.
Batch Process. The triglyceride is heated
with water at 150-250°C and 10-25 bar pres-
sure. The splitting is achieved in 6-10 hr,
depending on the nature of the triglyceride
feed, for example, the higher the molecular
weight of the triglyceride, the slower the split-
ting reaction. The reaction can be accelerated
by increasing the temperature; under high
pressure and at 225-260°C, no catalyst is
required.
A typical commercial batch splitting plant
(Lurgi) operates at 230°C/400 psig with over
96 percent split yields after two changes of
water to remove the glycerin by-product. The
sweetwater (glycerin/water mixture) is circu-
lated continuously from the base to the top of
the autoclave in this process. 10
A number of other batch fat splitting plants
is also available.
Continuous Fat Splitting Process.
Currently, continuous fat splitting is the most
widely used process in the industry. In the sin-
gle-stage splitting process, fat and water are
fed countercurrently into a continuous flow
column at up to 260°C/60 bar pressure condi-
tions. The glycerin by-product generated in
the splitting process is removed by water
(sweetwater), thus accelerating the reaction
equilibrium toward completion (Fig. 27.11 ). 10
The high splitting temperature ensures ade-
quate dissolution of the water phase in the fat
to the extent that mechanical forces for con-
tacting the two reactants are not required. The
fat phase passes from bottom to top through
the tower, with the void volume of the tower
acting as a reaction chamber. The water phase
travels downward through the mixture of fat
and fatty acid, concentrating the glycerin by-
product in the sweetwater phase. The top and
bottom sections of the tower are also designed
to effect the transfer of heat from the products
to the incoming reactant streams. Split yields
of up to 99 percent can be achieved by the use
of pre-purified fat/oil feedstocks.
 WA'IER

TO
VACUUM
PUMP
1
TO
HOTWELL

AIR
FAN

VI
0
)>
FATS
.:a
.,
~
.....
<
lr::d • STEAM )>
n
0
!II
POUSHING FillER )>
2
0
WAlER
VI
WAlER <
2
PRECOAT .....
MIXER :X:
~~---· STEAM m
::!
n
0
m
BLEACHED
.....
m
FATS :rJ
C)
m
2
fEB) FEED FEED PRECOAT TRANSFER .....
PUMP PUMP PUMP PUMP VI
PUMP
-'
Fig. 27 .9. Continuous fatty matter bleaching plant. (Courtesy G. Mazzoni S.p.A., Busto Arsizio, Italy) -'
-'
-'
 RCOOCH2
I
RCOOCH
I
ACOOCH2
Triglyceride
I
~
Enzyme
J
Saponification/
J
Direct
\II
Methyl Ester
Process Acidification Spliting Hydrolysis
Route Route Route

J~Lipase
tN~H
1"~
(H2S04)
JCH~ (CH30Na)

3RCOOH + glycerin 3RC00Na + glycerin 3RCOOH + glycerin 3RCOOCH3 + glycerin

l(H,SO<)

RCOOH
NaOH H;!()
(H2S04)

t
R::OONa + methanol RCOOH + methanol

lH:!B04l
RCOOH

Fig. 27 .10. Fat splitting processes.

Flashing
Splitting
....---+I~M:'I Tower

i1
Fat

Process Steam Fat Sweetwater Fatty Acid

Water
Fig. 27 .11. Single-stage countercurrent fat splitting plant. (Courtesy Lurgi GmbH, Frankfurt am Main,
Germany)
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
In summary, the continuous high-pressure
splitting of fats and oils involves:
1. The use of excess water to drive the reac-
tion to completion and for removal of
glycerin from the reaction zone.
2. The use of a proper combination of tem-
perature and pressure conditions to
increase the solubility of water in the fat
phase while maintaining the boundaries
of the fat/water interface. These condi-
tions also result in an increase in the rate
of splitting.
3. The possible use of an acid catalyst to
accelerate the reaction rate.
Saponification/Acidification Process. The
recovery of fatty acids from soapstocks and
soap reboil operations is of commercial value:
Triglyceride caustic refining•
(unrefined)
Triglyceride+ RCOONa (H2S04) • RCOOH
(soapstock)
RCOONa reboiling•
(impure soap)
RCOONa {HzS04) • RCOOH
(purified neat soap) (purified fatty acid)
The recovery of fatty acids from soapstocks
by a continuous process has been described:
soapstocks obtained from degumming and
alkali refining operations are subjected to a
saponification step followed by controlled
acidification for cost efficiency and pollution
control.Ila,b
The saponification/acidification route is
used for the manufacture of fatty acids that
are sensitive to excessive heat. The splitting of
castor oil with NaOH at 100-220°C followed
by acidification has been used to produce cas-
tor fatty acids. 12
Enzymatic Processes. The enzyme hydroly-
sis of triglycerides is catalyzed by lipases:
Triglyceride + 3H20
e~ 3RCOOH +Glycerin
Enzyme-based splitting of triglycerides is
under active development and offers the
1113
following advantages over modern steam
hydrolysis plants:
• the hydrolysis occurs under mild condi-
tions (35-37°C, ambient pressures)
• the color quality of the products ts
supenor
• the capital investment may be lower
• the split yields are equivalent
The selection of a suitable lipase for a
commercially viable process is based on the
following criteria:
• it should be nonspecific and nonselective
as to the structure of the triglyceride
• it should be stable at above ambient pro-
cessing temperatures, typically 45--65°C
• it should be economically viable (This
aspect has initiated a number of ongoing
studies on the recycling and immobiliza-
tion issues oflipase utilization for triglyc-
eride hydrolysis.) 14a,b
Methyl Ester-Based Processes. The fatty
methyl esters are produced predominantly by
the transesterification of fats and oils with
methanol in the presence of an alkaline cata-
lyst under very mild reaction conditions.ISa,b
They are used in the production of lauric-type
(C 12) alcohols. The short-chain fatty methyl
esters (C 8-C 10), produced as by-products via
the fractional distillation of crude lauric-type
(coconut, palm kernel) methyl esters, are con-
verted to fatty acids via acidic or alkaline
hydrolysis (Fig. 27.12). The hydrolysis of
short-chain fatty methyl esters by stream
splitting or Twitchell-type processes is not
very efficient because of unfavorable equilib-
rium constants. 16a,b
Fatty Acid Distillation
The removal of contaminants (unreacted
triglycerides, odor and color bodies, polymer-
ized matter, and decomposition products) from
split fatty acids is achieved by simple distilla-
tion.17a,b The products obtained from such
straight distillations are called "whole cut"
fatty acids (e.g., whole coconut fatty acid).
1114 RI~GEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

Triglyceride + CH30H - - - - > 3 RCOOCH 3 + glycerin

J
(Fractionation)

J
I
l
C-8 I C-10 Methyl Esters C-12+ Methyl Esters

(hyd•oly•;•l l(hyd•ogenat;on)

C-8 I C-10 Fattv Acids C- 12 + Fattv Alcohols

Fig. 27.12. Fatty acid production via methyl esters.

The separation of individual fatty acid
components from whole fatty acid distillates
is achieved by fractional distillation. 18 a,b
However, fractional distillation cannot effi-
ciently separate C 16-C 18 saturated from the
corresponding unsaturated fatty acids. In such
cases, the melting points vary considerably
with the degree of unsaturation and this prop-
erty is used for their separation via a number
of industrial processes. 19 a,b
Distillation. Straight distillation is used for
the removal oflow-boiling (top cuts) and high-
boiling (pitch or bottoms) impurities from the
crude split fatty acid stock. The distillation can
be done either in a batch or a continuous man-
ner. Generally batch distillation is employed
for small-capacity manufacturing; continuous
distillation is utilized for large-scale manufac-
turing and is highly automated (Fig. 27.13) 10
The split fatty acid (deaerated and preheated)
is sent to a distillation column (Fig. 27.13)
where it is vaporized rapidly by flowing over
heated trays under high vacuum (10 mbar)
with the addition of live steam (for fatty acid
circulation and reduction of the partiq} pres-
sure). The high boilers are removed by two
stages of entrapment: the high boilers and bot-
toms from the distillation column pass through
additional heated trays and a reboiler section to
vaporize residual fatty acids from the bottoms;
the light end condenser traps the low boilers
and the distilled product. The heavy "bottoms"
distillate is collected at the bottom section of
the still.
The distillation process is not used for the
narrow-cut fractionation. However, by pass-
ing a second time through the distillation
tower the main-cut distillates may be sepa-
rated into a light and heavy fraction; the light
end is collected at the top products section
and the heavy end is collected at the bottom
residue section of the still. The separation of
light and heavy fractions in the first pass is
possible for high lauric-type split fatty acids,
for example, coconut and palm kernel fatty
acids where the lower molecular weight
C6-C 10 fraction is "topped" from the heavier
cl2-Cl8 fraction.
The operation of a Lurgi fatty acid
distillation system 10 proceeds as follows. The
crude fatty acid is dried and degassed under
vacuum. This dried and deaerated crude fatty
acid is pumped into the distillation chamber
(vacuum of 10-12 mbar) that is divided into
5-10 chambers by vertical plates. Each
chamber is equipped with a heating element
and a baffle. Live steam is passed into the
system to effect recycling of the liquid
between the heating elements and the baffles
by the principle of an air-lift pump. The fatty
acid is sprayed on the baffles as a fine mist to
allow it to evaporate easily; non-vaporized
liquid is recycled from the bottom. The
fatty acid passes through each chamber,
from which it is discharged continuously.
 SOAP. FATTY ACIDS. AND SYNTHETIC DETERGENTS 1115

Vacuum

Light Ends

Crude Fatty Acid Distillate Residue Heavy Ends

Cross-Section of the
Stage 1 of the Stilt

Residue

Cross-Section
of the Still

Distillation Still

Heating Steam

Fig. 27 .13. Continuous fatty acid distillation plant. (Courtesy Lurgi GmbH, Frankfurt am Main, Germany)

The fatty acid vapor is condensed in the
surface condensers. Typical yields from the
fatty acid distillation process are:
Tops or head cut
Refined product
Residue
Fractionation. The separation of individual
components of a fatty acid mixture into high
purity fractions (98% +) is achieved by frac-
tional distillation. In a continuous fractionation
1-5% still the fractionation column can be equipped
85-91%
7- 11%
with trays, in the "Thormann" system, or with
the traditional packing to effect contact
 1116 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

Vacuum

Rectification Vacuum
Column I

Fraction I Ill II

Fig. 27 .14. Fatty acid fractionation. (Courtesy Lurgi GmbH, Frankfurt am Main, Germany)

between the upward-moving vapors and the years. 18a,b The majority of the recent work
downward-flowing condensing liquid states. falls in the following areas:
A ~ical high-efficiency fractionation sys-
• designs with gentle heating
tem (Fig. 27.14) consists of one continuous
• improvements in the column design to
straight distillation and one, or preferably two
fractionation columns. 10•I?a,b This system is reduce residence time
• e~ancements of system design to mini-
very efficient for the separation of low-
mize pressure drops
boiling fatty acid components,6•10 a C 12 fraction
• demister designs for better air/effluent
of 99.5 percent purity from coconut fatty acid
water pollution control
or a c22 fraction of 95 percent purity from
rapeseed fatty acid is readily obtained.
From an operational perspective, in rectifi- Special Separation Methods
cation column 1 of Fig. 27.14, crude fatty
T~e separation of long-chain saturated fatty
acid is dried and vaporized with the addition
acids (C 16-C 18 ) from the corresponding
oflive steam under a vacuum of 8-40 mbar. A
unsaturated fatty acids by distillation is not
mixed fraction is withdrawn from the column
practical because of the proximity of their
top. The product from the bottom of column 1
bo~ling points. However, both the melting
is vaporized in rectification column 2 with
pomts and the solubility (in organic solvents)
live steam under a pressure of 6-8 mbar. The
of these two types of fatty acids are vastly dif-
low-boiling fraction is collected in down-
ferent. 20 These properties are used to advan-
stream scrubbers after the vapor has been
tage for separating mixtures of saturated and
condensed in surface condensers.
unsaturated fatty acids into fractions that are
The separation scheme for coconut fatty acid
rich in either saturated (stearin) or unsaturated
is shown in Fig. 27.7. A variety of alternate
(olein) components.I9a,b
fractionation schemes can readily be devised.
Fatty acid distillation has been done for over Tallow fatty acid
100 ~ears.I?a,b However, most of the currently separatw~ Stearic acid + Oleic acid
practiced art has originated in the past several (Stearin) (Olein)
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
The following processes are used commer-
cially for the separation of such fatty acids:
mechanical pressing, solvent crystallization,
and hydrophilization.
Mechanical Pressing. This method, also
called panning or pressing, is the simplest and
oldest method, and is still practiced in many
developing countries. In this method, fatty
acids are melted in shallow pans and then
allowed to cool. The material transforms into a
crystalline solid with a liquid phase trapped
between the crystals of the solid phase. The liq-
uid portion (olein) is pressed, or squeezed out
by the application of mechanical force, sepa-
rating it from the solid (stearin) component.
The pressing can be done by hydraulic
presses in either a batch or a continuous
mode. A multiple number of melting/crystal-
lization/pressing cycles is utilized for obtain-
ing fractions of increased purity:
Tallow fatty acid first P~
Single press second pass.,
(Stearic acid)
Double press third pass._ Triple press
(Stearic acid) (Stearic acid)
The unsaturation, as determined by the iodine
value (IV), decreases from an IV of 10.0 for a
single press to an IV of 1.0 for a triple press
stearic acid grade.
Solvent Crystallization. Two processes, one
utilizing acetone (Armour) and the other
Cooling Wetting
Fatty Acid
Fig. 27 .15. Hydrophilization process for separation of olein and stearin. (Courtesy Lurgi GmbH, Frankfurt
am Main, Germany)
1117
employing methanol (Emery), are well known.
Using the latter, fatty acid is dissolved in
90 percent aqueous methanol in a 1 : 2 acid/
solvent ratio by the application of heat. The
resulting solution is then cooled to -l5°C
in a multi-tubular crystallization chamber
equipped with scrapers for efficient heat trans-
fer. The crystallized fatty acids are removed by
filtration. The filter cake is melted and
stripped of any residual solvent to yield the
refined stearin fraction, and then the liquid
stearin is converted to flakes or powder by a
variety of processes, for example, chill roller,
and the like. The mother liquor from the filtra-
tion is stripped to obtain the olein fraction. The
separated stearin and olein fractions have a
variety of commercial applications in both the
chemical and food processing industries.
Hydrophilization Process. In this process,
olein and stearin are separated by forming a
suspension of the stearin moiety in water with
the aid of a surfactant followed by filtration to
remove the stearin (Fig. 27.15). The mixture of
fatty acids is melted and then partially crystal-
lized by cooling. The resulting slurry, which is
a mixture of liquid olein and crystalline solid
stearin, is mixed with water containing a wet-
ting agent (sodium dodecylbenzene sulfonate,
sodium lauryl sulfate). After mixing for a spec-
ified period, the slurry is centrifuged; the light
fraction provides the liquid olein moiety, the
middle fraction is a suspension of solid stearin
in water and the lower fraction is a water/
surfactant solution. 10
Separating Washing
1118 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
Thermodynamically the fatty acid crystals,
after being wetted by the surfactant solution,
transfer from the liquid oil into the water solu-
tion. The oil droplets then coalesce to give the
lighter olein phase. The separated stearin is
remelted to remove residual water/surfactant
and then reprocessed to the desired level of
purity.
Although the quality of the final product
from these three processes is fairly compara-
ble, currently hydrophilization is the most
widely used process for the separation of
stearic and oleic acids.
SYNTHETIC DETERGENTS
Synthetic detergents were initially developed
to replace soap in an economy that was run-
ning short of edible fats and oils. It was soon
discovered that the synthetic compounds were
more resistant to hard water ions and provided
improved wetting and detergency over soap.
Over the years, the term "synthetic detergent"
has been shortened to "syndets" to describe
detergent compositions comprising synthetic
detergents, hard water control agents
(builders), and other detergent additives. The
term "surface active agent" has been short-
ened to "surfactant" to describe the surface
active ingredients. Since their introduction in
the 1940s, synthetic detergents have continued
to grow in both total volume and the percent-
age of detergent use as shown in Table 27 .2.
Whether in liquid or powdered forms, mod-
em detergent products are complex mixtures
of many different ingredients. Typical formu-
lations consist of surfactants, builders, and
other additives designed to maximize per-
formance for the consumer while maintaining
reasonable raw material and manufacturing
costs. Recent trends in both liquids and pow-
ders show increased use of multiple builder
and surfactant systems. 21 •22 Performance
additives such as bleaches, bleach activators,
enzymes, enzyme stabilizers, anti-redeposition
polymers, fluorescent whitening agents, dye
transfer inhibitors, and fabric softeners are
commonly used to increase overall per-
formance. Regardless of the product format
TABLE27.2 U.S. Consumption of Soap
and Synthetic Detergent
Synthetic
Soap Detergent
Year (MM lbs) (MMlbs) Total
1940 2306 30 2336
1950 2882 1443 4325
1960 1230 3940 5170
1970 1050 5650 6700
1980 1300 6400 7700
1990 1625 9000 10625
Source: SRIC's Chemical Economics Handbook, based
on a compilation from various sources. A personal
communication (08/14/02) from SRI states that because
of the variety of forms and concentrations in which
detergent products now appear, such data are no longer
available. Also, while soap production was relatively flat
for many years, it began to decline again in the late
1990s, as the liquid hand "soaps" and "body washes"
that are gaining market share are largely based on
surfactants. In contrast, the consumption of synthetic
detergents has continued to grow at a rate somewhere
between population and GDP growth.
or formulation type, surfactants play a critical
role in the cleaning process.
Characteristic Features of Surfactants
Surfactants have a characteristic molecular
structure consisting of one structural unit that
has very little attraction for the solvent
(lyophobic group), combined with a group
that has a strong attraction for the solvent
(lyophilic group). This duality is known as an
amphipathic structure. When a surfactant is
dissolved in a solvent, the presence of the
lyophobic group distorts the solvent liquid
structure, resulting in an increase in the Gibbs
free energy of the system. This acts to force
the molecules out of the solution in an attempt
to decrease the free energy of the system.
However, the presence of the lyophilic group
prevents the surfactant from being completely
expelled from the solvent. The opposing
forces give the surfactant molecule their sur-
face active properties. In aqueous solution, the
lyophilic group is known as the hydrophile and
the lyophobic group is called the hydrophobe.
Surfactant molecules are typically depicted
using a ball and stick representation as shown
in Fig. 27.16. The stick portion represents the
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1119

Tail Group
Head Group
(Hydrophobic or Lipophilic)
(Hydrophilic or Lipophobic)
Alkylphenol
Fatty Alcohol Ethylene Oxide
Propylene or Butylene Oxide Carboxylate
Fatty Amine Sulfate
Linear Alkylbenzene Sulfonate
Phosphate
Fig. 27 .16. Representation of surfactant amphipatic structure.

hydrophobic group or "tail" whereas the ball

represents the hydrophilic "head group."
Examples of common hydrophobes include
alkylphenol, fatty alcohol, and alkylbenzene.
Examples of common hydrophiles include
ethylene oxide (EO), sulfates, sulfonates, and
carboxylic acid groups. Depending on the
charged nature of the head group, surfactants
are classified as:
1. Anionic, the head group bears a negative
charge.
2. Cationic, the head group bears a positive
charge.
3. Zwitterionic, the head group has either a
positive or negative charge depending on
solution pH.
4. Nonionic, the head group bears no for-
mal ionic charge.
Aside from their ability to adsorb at inter-
faces, the most important aspect of surfactants
is their ability to form colloidal-sized aggre-
gates in solution. In dilute solution, the surfac-
tant molecules exist as individual hydrated
species. Increasing the concentration pro-
motes the formation of surfactant aggregates
or "micelles," as shown in Fig. 27.17. The con-
centration at which micelles start to form is
referred to as the critical micelle concentration
(CMC). Micelle formation is an important
phenomenon because interfacial effects such
as detergency and solubilization depend on the
existence of micelles in solution.
n ,.....
Fig. 27.17. Micelle formation in aqueous solution.
TABLE 27.3 Typical HLB Values for
Different Applications
HLBRange Typical Application
1-3 Reverse micelles
3-6 W/0 emulsifier
7-10 Wetting agent
8-18 0/W emulsifier
11- 15 Detergent
> 15 Solubilizing agent
Surfactant molecules can be tailored for use
in either aqueous or nonaqueous systems,
depending on their solubility characteristics.
The most common way to describe surfactant
solubility is the hydrophile- lipophile balance
(HLB). In the HLB method, a number is
assigned (0--40) related to the balance between
the water-loving (hydrophile) and lipid-loving
(lipophile) portions of the molecule. 23 •24 In
some cases the HLB number is calculated
from the structure of the molecule, in others it
is based on experimental emulsification data.
In general, there exists an optimum HLB for
different applications as shown in Table 27.3.
1120 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
Matching the HLB of the surfactant to that
of the application generally gives the best
performance.
For example, alkylbenzene is slightly surface
active in nonaqueous media but is insoluble in
water. Addition of a single S03H group to the
molecule imparts solubility and excellent sur-
factant characteristics in water but insolubility
in petroleum solvents. If alkylbenzene is di- or
trisulfonated, the compound becomes more
and more water soluble and loses much of its
surface activity. In both cases, the hydrophile
balance is exceeded with insufficient lipophilic
influence to cause micelle formation. However,
neutralization of the S0 3H group of a highly
water-soluble alkylbenzene sulfonic acid with
a long-chain amine produces an effective non-
aqueous surfactant. A similar effect of decreas-
ing water solubility and increasing nonaqueous
detergency can be achieved by increasing the
alkylbenzene carbon chain length from c,2 to
C 18 or higher.
Most commercial nonionic surfactants are
based on ethylene oxide (EO), which depend
upon a multiplicity of hydrogen and oxygen
bond linkages to effect the HLB. The carbon
chain length and degree of branching can be
varied to impact the hydrophobic characteris-
tics of the molecule. The degree of ethoxyla-
tion is used to control the hydrophilic nature
of the surfactant.
In surveying the literature, one might believe
that commercial surfactants are pure com-
pounds. In fact, commercially available com-
pounds are complex mixtures ofhomologs. For
instance, "lauryl sulfate" is a generic designa-
tion for a mixture of sulfates whose largest
fraction is derived from the c,2 alcohol but
also contains higher and lower alkyl chain
lengths. The homolog distribution depends
upon the alcohol source and degree of frac-
tionation. Alcohol ethoxylates are also com-
plex mixtures ofhomologs. Not only is there a
distribution of different alkyl chain lengths, but
EO adds to the alcohol according to a normal
distribution of adducts. Although it might seem
that a competitive advantage would be gained
by supplying a highly purified product, mix-
tures are frequently more effective than pure
compounds. Long experience with soaps and
synthetic detergents shows that except for
highly specialized purposes, pure compounds
are not competitive with commercial mixtures.
Synthetic Detergent Intermediates
Synthetic detergents are produced by various
chemical routes, using either natural and/or
synthetic sources as shown by the schematic in
Fig. 27.18. Natural sources include fats and oils
derived from vegetable and animal origins
whereas synthetic sources include crude oil and
natural gas. In many cases, the line between
what is natural and synthetic is ill defined.
The current world production of fats and
oils is around 65 MM metric tones of which
70 percent is of vegetable origin and
30 percent from animal sources. Oils with
high content of C 12 and C 14 fatty acids are
most commonly used by the detergent indus-
try and are readily obtained from coconut and
palm kernel. The most important animal fats
are lard and tallow, which contain primarily
C 16 and C 18 fatty acids. Fats and oils are com-
posed of fatty acid esters of glycerin called
triglycerides. Natural-based fatty acids pos-
sess an even number of carbon atoms and can
be either saturated or unsaturated. After
purification to remove phospholipids and
sterols, the triglyceride is treated with alkali
to produce soap and glycerin. Further treat-
ment of the soap with inorganic acids gives
the fatty acid. The fatty acid can be reacted
with methanol to give the methyl ester.
Alternatively, the triglyceride itself is treated
with methanol using a base catalyst to give
corresponding methyl ester and glycerin.
Crude petroleum oil consists of a complex
mixture of long-chain hydrocarbons. Natural
gas is a mixture of short-chain hydrocarbons
rich in methane, ethane, propane, and butane.
The exact composition of both depends on its
source. Crude oil and natural gas are processed
in different ways to give a variety of feedstocks
suitable for surfactant manufacture. The most
important feedstocks include ethylene, propy-
lene, paraffin, olefin, phenol, and benzene.
One of the major factors leading to the
development of modem synthetic detergents
was the industrial manufacture of fatty
alcohols. This was first achieved in Germany in
the 1930s using the sodium reduction process.
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1121

Fig. 27 .18. Sources of raw materials for surfactant production.

CH 20COR
50- 70°C
tHOCOR + 3 CHpH 3 R-COOCH 3 +
I
CH 2 0COR

200-250°C
R-COOCH 3 + H2 R-COH + CHpH
catalyst
Fig. 27 .19. Preparation of natural fatty alcohols.

While this process was commonly used until
the 1950s, it has been largely replaced by less
hazardous processes. Today, there are three
important technical processes for the manufac-
ture of detergent grade fatty alcohols: high-
pressure hydrogenation, the Ziegler process,
and the oxo-synthesis. 25 Numerous other
processes have been developed but are oflesser
technical and economic importance.
The most important process for the
manufacture of natural fatty alcohols is the
high-pressure hydrogenation of fatty acids or
their corresponding methylesters. Common
raw materials for the production of detergent
range alcohols include coconut, palm kernel,
palm stearin, soya, tallow, and lard. In the
methylester process, the crude oil is reacted
with an excess of methanol at 50-70°C to give
3 moles of methylester and 1 mole of glycerin,
as shown in Fig. 27.19. The reaction can be
accelerated using sodium methoxide as a cata-
lyst. The glycerol separates at the bottom of
the reactor after an appropriate reaction time.
The transesterification is complete when the
methylester no longer contains glycerin.
The hydrogenation reaction occurs at
200-350°C and hydrogen pressures of
250-300 bar. A variety of different metal
oxide catalysts have been used, however,
copper chromite is the most common. Under
these reaction conditions, the ester group and
any unsaturation are hydrogenated to give the
saturated fatty alcohol. It is possible to pro-
duce unsaturated fatty alcohols using various
1122 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

zinc catalysts. A number of different process
designs have been developed including the
fixed bed, the trickle bed, and the suspension
process. The various processes differ prima-
rily in the way in which the catalyst contacts
the feedstock and the specific catalyst used.
Both the oxo-synthesis and the Ziegler
process are based on petrochemical feedstocks.
The oxo or hydroformylation reaction was first
discovered in Germany in the late 1930s, but
was not used commercially untill948, by what
is now Exxon Chemical. The oxo process
uses a-olefins obtained from oligomerization
of ethylene, which are reacted with carbon
dioxide and hydrogen at 200--300 bar and
130-190°C, to give a mixture of linear and
branched aldehydes as shown in Fig. 27.20.
The resulting aldehydes are hydrogenated at
50--200 bar pressure and 150-200°C using
copper, zinc, or nickel catalyst to give the pri-
mary alcohol. Oxo alcohols contain both even
and odd carbon numbers and are more highly
branched than natural or Ziegler alcohols.
Using a conventional cobalt catalyst, the
amount of branching exceeds 50 percent.
The Ziegler process based on chemistry
discovered in the 1950s produces linear
primary alcohols with an even number of
carbon atoms. The main reaction steps are
shown in Fig. 27 .21. Triethyl aluminum can

130-190° c
RCH-CHO
I
200-300 bar CH 3

50-200 bar
RCH-CH2CH 20H + RC~-CHpH
150-200° c CH 3

Fig. 27.20. Oxo alcohol reaction chemistry.

Synthesis of triethyl aluminum

2AI +
Chain growth

Oxidation

R., . . R OR, ... OR

AI
I
R
+ t'
-- OR
Hydrolysis

Fig. 27 .21. Ziegler alcohol reaction chemistry.

 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
be prepared using a one-step or two-step
process. In practice, the one-step process
yields more by-products and is seldom used.
The reaction of triethyl aluminum with ethyl-
ene is highly exothermic. The distribution of
chain lengths follows a Poisson distribution
with only slight deviations due to competing
side reactions. The aluminum alkyls are oxi-
dized to the corresponding alkoxides using
dry air and hydrolyzed using water or sulfuric
acid to yield fatty alcohol. The Ziegler
process produces alcohol similar to that
obtained from natural sources.
Another key surfactant intermediate is
olefin, produced by thermal or catalytic
cracking of paraffin wax or alternatively from
oligomerization of ethylene. Olefins suitable
for surfactant production are primarily linear
with either terminal (a-olefins) or internal
(i-olefins) double bonds. Olefins produced
by the cracking process include a-olefins,
di-olefins, cyclic olefins, aromatics, and
paraffin wax. The major problem with the
cracking process is separation of the desired
olefins from the other by-products. Since the
mid-1960s, n-paraffins have been used as
starting materials for the manufacture of
n-olefins. Today, n-paraffins are obtained
from the distillation of paraffin-rich oils with
the use of molecular sieves. Molecular sieves
are aluminum silicates of the zeolite type. The
pore diameter of the zeolite used for paraf-
fin production is 5 A, which allows the
n-paraffins to enter the pore while the iso and
cyclic paraffins are removed by distillation.
Oligomerization of ethylene can be per-
formed in a number of different ways.
Reaction of ethylene with triethyl aluminum
using the Ziegler process consists of three
steps. The first step is the reaction of ethylene
with triethyl aluminum to give long-chain tri-
alkyl aluminum. The second step is the
transalkylation of the trialkyl aluminum with
ethylene (Alfol Process) or a long-chain
olefin (Ethyl Process) to give free olefin and
regenerate the trialkyl aluminum. The third
step is the separation of the olefin from the
undesired by-products.
A slightly different oligomerization method
is based on the Shell Higher Olefins Process
1123
(SHOP). The oligomerization reaction is car-
ried out on a nickel phosphine complex that is
separated and recycled by means of a solvent.
The reaction product consists of a-olefins and
i-olefins of different carbon chain lengths.
The i-olefins are fed to the purification, iso-
merization, and disproportionation stages to
obtain a wide range of a-olefins.
While olefins can be used directly to pro-
duce synthetic detergents, they are more com-
monly used as intermediate raw materials.
Alkylbenzene consists of a mixture of phenyl
substituted n-alkanes of 9-14 carbon atoms.
Prior to 1965, alkylbenzene was synthesized
from propylene tetramer, obtained by
oligomerization of propylene, and reacted
with an aluminum chloride or hydrogen fluo-
ride catalyst and benzene. The resulting "hard"
alkylate was a highly branched chain com-
pound. However, the slow biodegradability of
propylene tetramer-based materials became
apparent and by 1965, most of the detergent
industry had switched over to linear alkylben-
zene (LAB). Extensive research has demon-
strated biodegradation effectiveness in sewage
treatment plants in excess of95 percent.26--Z9
Today, there are two main routes for produc-
ing linear alkylbenzene. (Fig. 27.22) The
most prevalent route to alkylbenzene uses
partial dehydrogenation of paraffins, followed
by alkylation of benzene with a mixed
olefin/paraffin feedstock using liquid hydro-
gen fluoride (HF), aluminum chloride (AlC13),
or solid alkylation catalyst. The Pacol process
(paraffin conversion to olefin) uses n-olefins
produced from n-paraffins by dehydrogena-
tion over a heterogeneous platinum catalyst.
The Pacol process produces a small amount of
di-olefin, which lowers the LAB yield by
forming alkylate bottoms. The Define process
was developed to selectively hydrogenate di-
olefins to mono-olefins. A second older
process uses partial chlorination of paraffins,
followed by alkylation of the chloroparaffin
feedstock in the presence of an aluminum
chloride catalyst. Distillation is used to sepa-
rate alkylation reaction products into the tar-
geted detergent alkylate homolog distribution.
A coproduct stream of high molecular weight
linear alkylbenzene and dialkylbenzene is also
1124 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
2-PHENYL ISOMER
CHLORINATION
PARAFFIN _ . CHLOROPARAFFIN
+BENZENE
HF
OLEFIN + BENZENE ~ HIGH 2-$, LOW DAT
souo'G
ALKYLATION
CATALYST
Fig. 27 .22. Commercial alkyl benzene production.
produced for use in lubricant detergents and
industrial applications.
Products with low 2-phenyl isomer content
(13-22%) are produced by HF alkylation of
internal olefins from paraffin dehydrogena-
tion. High 2-phenyl products (25-35%) are
produced from AlC1 3 alkylation of
chloroparaffins or olefins from paraffin dehy-
drogenation. Super high 2-phenyl products
have been reported in the literature using
shape selective catalysts (>80%) but are not
commercially produced at this time.
Generally, high 2-phenyl products are pre-
ferred for use in liquid detergents due to
increased solubility. Low 2-phenyl products
are typically used in powder detergents but
can be used in liquid formulations with the
appropriate choice of hydrotrope.
Alkyl phenols are produced by reacting an
olefin with phenol using a strong acid
catalyst. The most common alkyl phenols are
4-ter-octylphenol, 4-nonylphenol, and 4-
dodecylphenol. Mono nonylphenol (MNP) is
by far the most common hydrophobe. It is
produced by the alkylation of phenol with
nonene under acid conditions. All commer-
cially produced MNP is made with nonene
based on propylene trimer. Because of the
skeletal rearrangements that occur during
propylene oligomerization, MNP is a com-
plex mixture of branched isomers.
DIALKYLTETRALIN (DAT)
AICI 3 HIGH 2-$
--+ HIGH DAT
LOW 2-$, LOW DAT
HIGH 2-$, LOW DAT
Anionic Surfactants
Alkylaryl Sulfonates. Alkylbenzene sulfonates
have been the workhorse of the detergent
industry for more than 40 years. They account
for approximately 50 percent of the total syn-
thetic anionic surfactant volume. Three basic
grades of alkylate (alkylbenzene) are manu-
factured with molecular weight ranges of
approximately 235, 240, and 260. In general,
the lower molecular weight range alkylates
are used for light duty liquid (LDL) systems
whereas the higher molecular weight grades
are used in heavy duty liquids (HDL) and
heavy duty powder (HDP) detergents.
Sulfonation. For detergent applications, the
alkylate must be sulfonated and then neutralized
with a base such as sodium hydroxide to give a
concentrated slurry, typically called "paste."
The major uses of the paste are in the produc-
tion of spray-dried powders and in both light
and heavy duty liquid detergents. The paste can
also be drum-dried to a powder or flake, or
spray dried to light-density granules. Dried
forms of LAS are used primarily for industrial
and institutional cleaning applications.
Oleum and sulfur trioxide (S0 3) are
commonly used for sulfonation, with the
latter growing in popularity in recent years.
Oleum sufonation requires relatively inexpen-
sive equipment and can be run as batch or
 SOAP. FATTY ACIDS, AND SYNTHETIC DETERGENTS 1125

continuous processes. However, the oleum A typical batch oleum sufonation process is
process has major disadvanta ges in the high shown in Fig. 27 .24. Four basic unit operations
S0 3 cost/lb (as H2S04), the need for spent are utilized prior to neutralization: sulfonation,
acid stream disposal, and the potential corro- digestion, dilution, and phase separation.
sion problems due to sulfuric acid generation . Mixing of the alk:ylate and oleum is done in
The chemical reactions involved in oleum sul- the sulfonation stage. Heat removal from the
fonation are shown in Fig. 27.23. Typically, highly exothermic reaction is achieved by
the oleum process yields 88-91 percent purity reactor jacketing and/or recirculating heat
sulfonic acid with the remainder consisting of exchanger loops. Key variables in controlling
approximately 6-10 percent sulfuric acid and alk:ylbenzene conversion and acid color are the
0.5-1.5 percent water and 0.5-1 percent temperature, acid strength, reaction time, and
unsulfonated oils. the ratio of oleum to alk:ylate. The product

~so,H +
~+ R
R

rBYS 0 3H+
H2S04 + 3 NaOH ____. ~

R
Fig. 27 .23. Oleum sulfonation process.

Oleum~--..,

Acid Settler
Alkylate - - . . . , Surge Tank

Oleum Reactor
Spent Acid

Water

NaOH - - - - - - - - + 1

Neutralizer

Finished Slurry

Fig. 27 .24. Batch oleum sulfonation process.

1126 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
leaving the sulfonation zone is aged or
digested 15-30 min to allow reaction comple-
tion. At this point in the process, the reaction
product consists of a mixture of sulfonic and
sulfuric acid. Following digestion, the mixture
is diluted with water to quench the reaction.
The reaction product is then fed to a separator
to allow for gravity settling of the spent sulfu-
ric acid layer from the lighter sulfonic acid.
The separation time is dependent upon the
separator vessel configuration, sulfonic acid
viscosity, temperature, and the degree of aera-
tion in the feed streams.
The gaseous air/S0 3 sulfonation process
normally generates a product composed of
@(so~ +
R
R ~s-o-s
~1111
11 II 0 0--®- R +
0 0
H2 S04 + 3 NaOH
Fig. 27 .25. Sulfur trioxide sulfonation process.
Alkyl Benzene
Air/S03
Digestor
Fig. 27 .26. Alkyl benzene sulfonation process.
95-98 percent sulfonic acid, 1-2 percent sulfuric
acid, 0.5-1 percent water, and 1-2.5 percent
unsulfonated oils. Although the initial capital
costs are much higher than those for an oleum
process, relative sulfonic acid yields and spent
acid disposal costs are substantially lower. The
chemical reactions involved in air/S03 sufona-
tion are shown in Fig. 27.25. The S03 sulfona-
tion reaction differs from oleum in that the
reaction product consists of a mixture of sulfonic
acid and the anhydride. The anhydride is reacted
with water to produce 2 moles of sulfonic acid.
A typical continuous air/S0 3 sulfonation
process is shown schematically in Fig. 27.26.
Sulfur trioxide is produced from vaporization
R --©--~s-o-s~-®- R
II II
0 0
+ H,O
Product
Caustic Soda
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
of liquid so3 or generated on-site by burning
sulfur and then catalytically converting S0 2 to
S0 3 over a vanadium catalyst. Increased ship-
ping regulations and sensitivity to storage of
the highly hazardous liquid so3 has increased
the trend toward on-site sulfur trioxide genera-
tion. The vaporized S03 is diluted to 4-8 wt
percent in dry air prior to sulfonation. The air
serves as a diluent and heat sink for the highly
exothermic sulfonation process. In the sulfona-
tion reactor, the molar ratio of SO/alkylate is
controlled between 1.03/1.0 and 1.0/1.0 to
achieve optimum conversion to sulfonic acid
without increased side reaction or color degra-
dation. The Chemithon,30•31 Ballestra,3 2 and
Mazzoni33 reactor designs each have unique
falling film designs to provide intimate mixing
of the alkylate and the air/S0 3 streams. The
reactor temperature is controlled between 110
and 150°F, depending on the desired produc-
tion rates and product quality targets.
Digestion and hydrolysis temperatures are con-
trolled between 110 and 125°F. During hydrol-
ysis, approximately 2 parts of water per 100
parts of reaction product are added to convert
acid anhydrides to sulfonic and sulfuric acid.
Both the oleum and S03 sulfonation processes
are quite exothermic and almost instantaneous.
In order to prevent decomposition and main-
tain optimum product color, an efficient reac-
tor heat removal system is necessary.
Cold sulfonation is also practiced using S02
as a solvent and refrigerant. 34•35 The sulfonic
acid color is low because of low reaction tem-
perature and rapid removal of the reaction
exotherm via S02 vaporization. Equipment
consists of fairly simple glass-lined reactors
equipped with gaseous S02 recovery. Purging
of S02 from the reaction product and control of
S0 2 recovery are key to achieving a high-
quality product. As in the case of air/S0 3 sul-
fonation, this process can be used to produce
R-OH +
Fig. 27.27. Sulfation of alcohols and alcohol ethoxylates.
1127
all detergent-grade surfactants including alkyl-
benzene, alcohol, and alcohol ethoxylates.
The Chemithon Corporation has patented a
novel venture reactor. 36•37 The organic to be
sulfonated is injected into a stream of gas con-
taining S03 at a venture. The reaction mixture
is quenched and recycled downstream until
sulfonation is complete. The reactor design
can be used for highly viscous, high molecular
weight specialty surfactants for industrial
applications such as lubrication oil additives.
Neutralization of sulfonic acid is similar
regardless of sulfonation process. The sulfonic
acid can be neutralized with an aqueous solu-
tion of NaOH, KOH, NH40H or with alka-
noamides. The sodium salts are used for
formulating spray-dried powders for household
laundry consumption. Ammonium and alka-
nolamine salts are commonly used in light duty
liquid detergents. In general, neutralized salts
from oleum sulfonation contain approximately
8-10 percent sodium sulfate whereas those
from air/S0 3 sulfonation contain only 2-3 per-
cent sodium sulfate. Sulfonic acid can also be
processed to a dry powder form by in-situ
neutralization with a base salt, such as sodium
carbonate. The neutralized sodium salt can be
dry blended with other detergent additives to
produce a free flowing powder detergent.
Sulfation. For the sulfation of alcohols or alco-
hol ethoxylates, falling film reactors are also
used, however, cooling water and sulfation tem-
perature are adjusted to lower values for these
materials. The digestion and hydration steps are
not required in sulfation and these systems are
bypassed. The acids are neutralized immediately
to minimize degradation and side reactions in
storage. Typical S03 sulfation reactions for
alcohols and alcohol ethoxylates are shown in
Fig. 27.27. Typical processes for air/S0 3 sulfa-
tion of fatty alcohols is shown in Fig. 27.28.
1128 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

To Scrubber

Cyclone
Fatty Alcohol Product

Air/S03

Caustic Soda -----J

Fig. 27 .28. Fatty alcohol sulfonation process.

Nonionic Surfactants a~~ _molecule containing an active hydrogen

Nonionic surfactants are increasingly popular (tmbator). The alkoxylation reaction is best
active ingredients. The majority of nonionic described as a two-step process. In the first
surfactants are ethylene or propylene oxide step, the catalyst forms a charged complex
derivatives of alkylphenols or fatty alcohols, with the initiator. In practice, the reaction is
usually run using a base catalyst to avoid creat-
although fatty acids, alkyl amines, and alka-
ing a large amount of polyethylene glycol
nolamides are commonly used. In general, one
(PEG) and other by-products. Alcohol and
ethylene oxide unit is required to solubilize
nonylphenol ethoxylates are two of the most
each methylene unit in the hydrocarbon tails.
common types of nonionic surfactant. The
By changing the ratio of ethylene oxide to fatty
reaction chetnistry for the alcohol ethoxylate is
groups, the nature of the surfactant can be
shown in Fig. 27.30. The degree of ethoxyla-
modified from oil-soluble to water-soluble
a normal Poisson distribution.
products. This versatility makes applications tion follows
In processing, the initiator and catalyst are
possible in numerous areas, such as detergents,
charged to a reactor and purged with an inert
agricultural products, corrosion resistance for
gas such as nitrogen. The partial pressure is
metals, emulsion polymerization, textile appli-
so that the explosive litnits of the gas
cations, deinking, and the like. Fatty alcohols adjusted
in the reactor during and after
are among the most useful intermediates for mixture
addition of the oxide are not exceeded. The
the production of nonionic surfactants, some of
reaction tnixture is heated to 115-200°C and
which are listed in Fig. 27.29. Discussion of
the oxide is added until the desired pressure is
each and every surfactant listed is beyond the
reached. Heat removal rates control the rate of
scope of this work. Only the major surfactant
reaction. Excessive cooling can result in
classes will be covered. A more complete dis-
excessive absorption of oxide into the reac-
cussion of different surfactant classes and their
tion tnixture, which can result in a sudden
properties is available. 38
reaction followed by overpressure. The
Ethoxylation. Ethylene and propylene oxide reaction temperature and pressure are con-
are highly reactive species that will react with trolled until the desired quantity of oxide has
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1129

Fig. 27 .29. Surfactants obtained from fatty alcohols.

R-OH + NaOH

0
R-OtCH2CH20-] Na+ + H/-CH2 -
n

R-OH + R-ofcH 2 cH 2 o ] Na+

n

Fig. 27 .30. Fatty alcohol ethoxylation chemistry.

been added. The batch is then cooled and the
catalyst neutralized with a Lewis acid or
removed by filtration.
Amphoteric Surfactants
These surfactants contain both cationic and/
or anionic groups on the same molecule.
Amphoteric surfactants are relatively expen-
sive due to the raw material and processing
costs. Typical applications include liquid dish-
washing detergents, shampoos, body wash, and
other personal care applications. In general,
amphoteric surfactants detoxify and mitigate
the irritation of anionic surfactants in the for-
mulation. A typical reaction scheme for coco
1130 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

Fig. 27 .31. CAPB reaction chemistry.

amide propyl betaine is shown in Fig. 27.31. • a contribution to final product alkalinity
Other examples of amphoteric surfactants • buffer capacity in the desired pH range
include amine oxides, amphoacetates, and • deflocculation capability
amino propionates. A detailed discussion of the • compatibility with other formulation
various different types of amphoteric surfac- ingredients and detergent additives
tants and their properties is available. 39,40 • consumer safety
• environmental acceptability
Cationic Surfactants • processibility
Cationic surfactants tend to be specialty items • adequate cost/performance
that are tailored for diverse uses such as In today's detergent products, a variety of
germicides, textile applications, corrosion builder materials are used singly or in combi-
inhibitors, and fabric softeners. Their primary nation with other builders to contribute
growth has been in fabric softeners for home unique properties for final product perform-
laundry detergents. Because cationics are anti- ance enhancement.
static agents, they perform well in removing
static charges associated with synthetic fabrics. Phosphates. Tetrasodium pyrophosphate
Cationic surfactants have at least one (Na4 P20 7 ; TSPP) became commercially
hydrophobic group attached directly to a pos- available in the mid-1930s and soon gained
itively charged nitrogen atom. Cationic sur- acceptance as the preferred builder for soap
factants may be formed from nitriles, amines, formulated products. The combination of
amidoamines, or quaternary nitrogen bases. TSPP and soda ash was more effective than
Significant literature reviews cover this sub- either ingredient used separately. By the mid-
ject in great detail. 41 -4 3 1940s, sodium tripolyphosphate (Na5P30 10;
STPP) was commercially available and had
Detergent Builders supplanted TSPP as the preferred builder
because of superior detergent processing, sol-
Builders are typically added to a detergent
ubility, and hard water sequestering proper-
formulation to extend or improve the cleaning
ties. Sequestration is defined as the reaction
performance of a formulation across a wide
of a cation with anion to form a soluble com-
range of use conditions. The combination of plex. The sequestration of ca++ and Mg++
builders and surfactants exhibit a synergistic
ions leads to softened water, which results in
effect to boost total detergency and cleaning
better surfactant solubility and improved
efficacy, as compared with an equal amount cleaning performance. STPP was the major
of either compound alone. The major proper- builder ingredient in heavy duty laundry
ties and characteristics that are desirable for detergents until the 1970s when phosphates
a compound to be considered a detergent were blamed for eutrophication of lakes and
builder include: streams and thus has been almost completely
• the ability to control water hardness and removed from commercial laundry deter-
other metal ions gents. STPP is still widely used in automatic
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS
dishwashing detergents and in I&I cleaning
applications.
Other possible builder salts include
tetrapotassium pyrophosphate, sodium
trimetaphosphate, trisodium and tripotassium
phosphates, and sodium acid pyrophosphates.
Significant literature reviews cover this sub-
ject in great detail. 44•45
Silicates. Both sodium and potassium sili-
cate solids or solutions have valued function-
ality including emulsification, buffering,
deflocculation, and anti-redeposition ability.
Silicates also provide corrosion protection
to metal parts in washing machines, as well as
to the surfaces of china patterns and metal
utensils in automatic dishwashers. Silicates
are manufactured in liquid, crystalline, or
powdered forms and with different degrees
of alkalinity. The alkalinity of the silicate
provides buffering capacity in the presence
of acidic soils and enhances the sequestra-
tion ability of the builder system in the
formulation. The silicate/alkali ratios of the
silicates are selected by the formulator to
meet specific product requirements. Silicate
ratios of 111 are commonly used in dry blend-
ing applications while silicate ratios of 211
and higher are commonly used in laundry and
autodish applications.
Carbonates. In most areas of the United
States, phosphates have been legally banned
from use in home laundry detergents. Sodium
carbonate, commonly called soda ash
(Na2C03), or a combination of soda ash and
zeolite has replaced STPP as the builder in
granular laundry products. Sodium carbonate
softens water by precipitating hardness ions
as insoluble carbonate salts. It is one of the
most economical sources of alkalinity for
detergents and provides some degree of soil
dispersion and suspending action. Sodium
carbonate is commonly used in powder laun-
dry detergents, autodish powders, and hard
surface cleaners.
Sodium Citrate. Sodium citrate
(Na3C6H250 7) has builder characteristics due
to its ability to sequester hard water ions and
1131
deflocculate soils. Sodium citrate's principal
use is in liquid detergents and personal care
products.
Zeolites. Zeolites are an important alterna-
tive builder for powdered laundry detergents
and structured surfactant systems. Zeolites
are crystalline hydrated aluminosilicates of
Group I and Group II elements. They are a
complex mixture of sodium, potassium, cal-
cium, and magnesium salts, and appear in
natural and synthesized forms. Zeolite 4A
(N~ · A1p 3 · 2Si0 2 · 4.5Hp, commonly called
Zeolite A) is the most widely used form for
laundry detergents.
Zeolites are not water soluble but they reduce
calcium water hardness by ion exchange. The
calcium ion passes through the zeolite pore
openings and exchanges with the sodium ion.
Magnesium ions are not significantly removed
by zeolites because of the large atomic radium
of the Mg++ ion. Zeolites are commonly used
in combination with other builders such as
sodium carbonate to control magnesium and
other ions present in the wash water.
Sodium Nitrilotriacetate. One of the first
compounds developed as a replacement
for STPP was sodium nitrilotriacetate
(N(CH2COONa)3 ·H20; NTA), which has
excellent sequestration and/or chelating proper-
ties. This product was quickly accepted by the
detergent industry as an alternative builder.
However, its use in detergents was suspended in
the United States in 1970, when three major
detergent manufacturers voluntarily agreed to
discontinue its usage due to preliminary data
suggesting that the compound could be terato-
genic. Subsequent assessment by the EPA indi-
cated that the risk to persons exposed to NTA
from detergents is not significant. However, the
EPA stated that NTA should not be used in
products such as shampoos, hand-dishwashing
detergents, foods, or other consumer products
designed for direct dermal or oral exposure.
Although NTA has not been used in U.S. house-
hold laundry products since the voluntary ban,
it has been widely used as a detergent builder in
Canada since 1970, and in the United States
in I&I cleaning products. NTA is normally used
1132 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
in liquids as the primary builder or in combina-
tion with phosphates in spray-dried detergents.
Detergent Additives
In addition to detergent builders and surfac-
tants, there are a number of different additives
that perform specific functions in the detergent.
Sodium Sulfate. Although considered a
weak builder by some manufacturers, sodium
sulfate (Na2 SO4) contributes little to deter-
gent performance. It is commercially avail-
able from natural sources and as a by-product
from rayon processing. In dry mix and
agglomerated type products, sodium sulfate is
used to improve finished-product flow char-
acteristics. In spray-dried products, sodium
sulfate acts as an inert filler and aids in den-
sity control.
Sodium Chloride. Sodium chloride (NaCl) is
used by some detergent manufacturers, its main
function being as an inert filler or diluent. In
spray-drying operations, NaCl is used to con-
trol crutcher slurry viscosity and the density of
the spray-dried bead or granules. In liquid
formulations, NaCl is used to control product
viscosity through the salt effect. Although salt
is used to some extent in autodish formulations,
it is not recommended because of potential
machine and dishware corrosion.
Anti-Redeposition Polymers. The surfactants
employed in synthetic detergents are effective
in removing soil and stains from the surface of
the washed fabric. Under heavy soil loading,
there is a tendency for these soils to redeposit
on the fabric. Various charged polymers have
been found to prevent soil redeposition.
Sodium carboxymethylcellulose (NaCMC) is
effective in reducing soil redeposition at for-
mulations level of 0.1-0.5 percent. The
sodium salt of polyacrylic acid is also an
effective anti-redeposition polymer. Molecular
weights of 5000 gm/mol give a good combina-
tion of performance handling characteristics.
Copolymer of styrene and maleic anhydride
are also commonly used, although the opti-
mum molecular weight is approximately
45,000. The polyacrylates are typically used at
0.5-1 percent in the formulation.
Optical Brighteners. Although the surfac-
tant system in formulated detergents are effec-
tive at cleaning clothes, white fabrics tend to
gray or lose the white appearance after multi-
ple wash cycles. Optical brighteners are added
to detergent formulations to visually improve
the whiteness or brightness of the fabric.
All major liquid or powdered detergent prod-
ucts contain one or more fluorescent whitening
agents. 46 Substantive to most fabrics, these
materials absorb ultraviolet radiation and con-
vert it to visible blue-white light that masks the
natural yellowing or graying of the fabric.
Most brightener systems are more effective on
cotton than on synthetic fabrics. The usage
range varies from 0.05 to 0.2 percent in the
detergent formulation.
Hydrotropes. Hydrotropes are used primarily
in liquid detergents to increase the solubility of
sparingly soluble ingredients and improve
storage stability. They are also used occasion-
ally as viscosity modifiers in the slurry phase
of manufacturing spray-dried detergent pow-
ders. Reduction of the detergent slurry viscos-
ity improves its processing characteristics,
reduces product bulk density, and insures crisp,
free-flowing granules. The most common
hydrotropes are the ammonium, potassium, or
sodium salts of toluene, xylene, or cumene
sulfonates.
Enzymes. A number of different enzymes
have been developed for use as adjuvants in
detergent systems to remove common soils
and stains. Protease enzymes are used to
cleave protein-based soils into smaller pieces
more easily removed by the detergent system.
Lipase enzymes are used to cleave lipid bonds
resulting in fatty acid and glycerol. Lipase
enzymes work better at elevated temperature
and tend to become active in the drying oper-
ation. Noticeable removal of stains occurs
after multiple wash cycles. Amylase enzymes
tend to break carbohydrate bonds in sugar-
based soils. Cellulase enzymes are designed
to remove micro fibulas in cotton fabric to
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1133

help retain color intensity and appearance. advantages of spray drying are numerous: the
Enzymes are available in liquid and powder product density can be varied from 0.20 to
form. Care must be taken when handling solid 0.80 gm/cm3, the detergent granule solubility
enzymes to ensure that the powder does not is significantly improved, very high produc-
become air borne where it can be inhaled by tion rates are easily achieved, and multiple
production workers. Enzymes are used in formulations can be prepared using the same
both liquid and powder laundry detergents. equipment. The major disadvantages of spray
drying are the initial capital investment
Pearlescent-Opacifying-Thickening Agents. required and the energy intensive nature of
These compounds are used in liquid detergent the process. Spray drying involves several
systems to produce a specific aesthetic effect. processes: selection of formulations, slurry
Pearlescent compounds, such as mica or ethyl- preparation, atomizing, drying conditioning
ene glycol distearate (EGDS), are added to of the product, post-additions, packaging,
give a luxurious appearance to liquid formula- waste reclamation, and pollution control.
tions. Opacifying agents include water-soluble Spray-dried powders are formulated to give
salts of styrene and maleic anhydride and are the best overall cleaning performance and
used to reduce translucence, modify the vis- flow characteristics at the lowest possible for-
cosity characteristics of liquids, and provide a mulation costs. Typical spray-dried detergent
cream-like texture to the product. Polymeric formulations are shown in Table 27.4. Slurry
thickeners and clays are used to modify the preparation is considered to be the single
rheological properties of liquids for various most important factor in spray drying.
applications where cling to vertical surfaces is Control of the raw material order of addition,
beneficial. slurry solids level, slurry temperature, viscos-
ity, and aeration enables manufacturers to
Anticaking Agents. The use of non- deliver the desired final product characteris-
phosphate builders in laundry powders has tics. The spray tower itself is simply a con-
changed the flow characteristics and caking tained heat source that removes moisture at
tendencies. Products formulated with a uniform rate dependant upon the quality
increased anionic surfactant levels and higher and the quantity of feed to the dryer. If feed
sodium carbonate content tend to exhibit variables are not controlled, variability in the
compaction in storage. Anticaking agents density and moisture levels of the powder will
have been added to the formulation to reduce
this tendency, especially in warm, humid cli- TABLE 27.4 Spray-Dried Detergent
mates. A wide variety of products are avail- Formulation
able, including sodium benzoate, tricalcium
Phosphate Built Non-Phosphate
phosphate, colloidal aluminium oxide, silicon
Detergent Built Detergent
dioxide, magnesium silicate, calcium stearate, Ingredients wt% wt%
and microctystaline cellulose.
Sodium 20-35 0
Tripolyphosphate
Spray Drying. A major portion of powdered Sodium Carbonate 5-10 5-10
laundry detergents is spray dried. In this Zeolite A 0 0-20
process, the detergent raw materials are mixed NaLAS 0-15 0-20
with water to form a thick paste or slurry, Alcohol Ethoxylate 0-15 0-20
atomized into spherical droplets, and dried to NaAES 0-5 0-5
Sodium Silicate 3-6 3-6
produce a free-flowing granular product. The Sodium Sulfate 10-30 10-30
art of spray drying was first patented in 1883, NaCMC 0 0.1-1
but was not practiced to any extent until the Enzymes 0.1-1 0.1-1
1930s. With the advent of synthetic detergents Optical brightener 0.1-0.3 0.1-0.3
in the 1940s, spray drying became the domi- Bleach 0-5 0-5
Water 3-8 3-8
nant method of detergent processing. The
1134 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY

vary. For example, if the slurry solids level is general, a countercurrent tower will produce a
not constant ( ± 2%), the evaporative load, higher density particle than the concurrent
production rate, particle sizing, and moisture type. In countercurrent systems, the heated
levels of the spray-dried granules will vary. gas stream (250-270°C) is uniformly dis-
Compensating for nonuniform feed to the persed into the lower section of the tower
spray tower is difficult because of the interac- through a series of plenum chambers or baf-
tion of control variables such as tower tem- fles equally spaced around the unit's periph-
perature, pump pressure, gas velocity, and so ery. The hot gases are cooled as they exhaust
on. Although some minor tower adjustments the top of the tower by the drying of atomized
are possible, the major control for routine detergent droplets upon contact with the hot
production is consistent and uniform prepara- air stream. Because of the relatively low tem-
tion of the detergent slurry. perature (11 0-140°C) at this point in the
Slurries are prepared via batch, semi- tower, the particles do not expand to their full
continuous, and continuous crutching units. capacity as water evaporates. This lower
Solids levels are normally kept as high as expansion rate results in a bead with
possible ( 64-72%) to reduce the heat increased bulk density and thicker shell. If a
requirements and maximize the tower similar formulation were dried in a concurrent
throughput. After the detergent raw materials spray tower, the higher temperature
are mixed, the slurry is charged to a homoge- (250-270°F) and increased drying rate would
nizer and any large lumps or gritty particles increase the evaporative rate and result in a
are desized and screened to prevent plugging thin-walled bead of lighter density.
of the spray nozzle. The slurry is then charged In most spray towers, the airflow rate and
to a booster pump, deaerated, and sent to a the temperature are adjusted at the inlet ports
high-pressure pump (300-120 psig) for atom- to maintain balanced air/temperature patterns.
ization. Most detergent slurries are atomized When the atomized slurry is sprayed into the
into spherical droplets via high-pressure noz- drying chamber, the airflow pattern is dis-
zles. The nozzles produce a hollow conical turbed and becomes very turbulent. This
pattern with a spray angle of 45-90°. The effect can cause localized temperature gradi-
slurry emerges from the nozzle as a film, ents (hot or cold spots) and impact the parti-
which is sheared into droplets by the centrifu- cle drying characteristics. It is possible to
gal force developed by specially grooved have both over and under dried particles dis-
cores inserted into the nozzle before the dis- charged at the same time from the tower
charge point. A series of spray nozzles (2-25) because of poor adjustment of the airflow in
are placed near the top of the spray tower and the tower. Adjustment of the airflow patterns,
angled so that one edge of the desired spray as well as sending a balanced spray into the
pattern is vertical to the spray tower side tower, can help counteract this situation.
walls. Some spray towers use two or three Increased impingement of the product on
rings of nozzles, depending upon the formu- the tower walls is another negative effect
lation and drying capacity of the unit. of excessive turbulence and of excessive
Production rates of detergent spray towers spray nozzle velocity. A ring of the product
range from 5000 to 80,000 lbs/hr. In most may form approximately 10-20 ft below the
cases, the rates are controlled by the slurry spray nozzles and build in size until it cracks
feed facilities, solids levels, and the drying or scales off the walls. Ring removal methods,
capacity. A schematic of a typical spray- such as periodic cleaning using air or water
drying facility is shown in Fig. 27.32. Spray lances, vibration or sonic shocks, or mechan-
towers vary in size from approximately 10 to ical cleaning rings, are sometimes used to
35 ft in diameter and range from 40 to 200 ft prevent a buildup that could result in blockage
in height. The majority of detergent spray of the tower discharge.
towers use countercurrent airflow patterns After drying in the spray tower, the detergent
although some use a concurrent design. In granules are conveyed to storage silos prior to
 CtKJie For Clean•ng Ru-.g
, .. ... . . .. ~:-· Tid

oo Detergent l ~n!
slurry

(I)
Dose• Con1•nuou10 Feed•ng S vstt:m 0
l>
Ltqu•d Feed :a
Sol<ls Feed ~~
~-i
<
l>
Q
~-t~t )t.(; c
(I)
~! ~
Conhnuous Crutcher j~
l>
~· 'i Agong Vessel j?ij : 2
•... . H1gh Pfessure Pump I! ', c
(I)
P.tnel 8oatd !(_ ;; 9Folters - , tJ L__
Y . ,.": ir.!t'\Fdcers <
; . Homogemzer t.. . .&..o· - \. ""'.. , . 2
-i
:I:
Fig. 27 .32. Spray tower and slurry preparation. m
-i
0
c
m
-i
m
::1:1
C)
m
2
-i
(I)

......
w
Ul
1136 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
packaging. In some processes, product storage
is preceded by fluid-bed conditioning. The
product for the tower is very warm
(75-120°C) and typically contains moisture
levels of 1-3 percent. Conditioning is
employed to prevent caking or product-flow
problems due to either the high temperature or
excessive free moisture content. Following
conditioning, perfume and other heat-sensitive
ingredients (enzymes, surfactants, bleaches)
may be added to the product. Post-addition is
accomplished by metering the additives into
the spray-dried base in a rotary drum or other
mixing device. The post-additions normally
comprise 2-15 percent of the total detergent
formulation. An excellent review of spray dry-
ing and key patents is available. 47 •48
Agglomeration Processing
Agglomeration is a technique of binding
a mixture of granular and/or dry, powdered
raw materials into an attractive granular form
with enhanced aesthetic and flow characteris-
tics. The majority of granular automatic-
dishwashing compounds (ADWCs) and some
laundry powders are manufactured using the
agglomeration process. The advantages of
agglomeration are low capital costs relative to
spray towers and reduced energy consumption.
Agglomeration also yields a higher-density
Dry Liquid
Premixing
l
Agglomeration Conditioning
Fig. 27 .33. Unit operations for batch agglomeration.
product, which can result in reduced pack-
aging costs. The major disadvantage of
agglomeration is a limitation in surfactant
loading due to raw material absorption
characteristics, particularly in laundry appli-
cations. As energy costs have assumed
increasing importance, and higher-density
products have gained in popularity, agglom-
eration or combinations of agglomeration
and spray-drying technologies have found
wider use.
The typical process steps for formulating a
laundry or auto-dish detergent are usually
defined in the laboratory prior to continuous
plant processing, however, they generally
follow the scheme shown in Fig. 27.33.
Frequently, the dry raw materials are pre-
mixed and then metered into the agglomera-
tion equipment. In the agglomerator, the
surface of the dry raw materials is exposed to
atomized sprays of surfactant or silicates to
begin building the agglomerated particle.
Following addition of liquids to the dry raw
materials, the product has a wet or pasty tex-
ture and requires conditioning to remove
excess water prior to storage or packaging.
Conditioned agglomerates are screened to
remove oversize particles and then blended
with other additives (bleaches, enzymes, dyes,
and perfumes) that would not be stable under
agglomeration conditions.
Post Addition
Packaging
Drying
(optional)
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1137

-Liquid Spray Header

Motor
Driv e l
Product Discharge
Product Continuous
Discharge
Batch

Fig. 27 .34. Batch or continuous ribbon mixer.

Numerous equipment types can be used for

agglomeration, including horizontal ribbon,
vertical mixers, rotary drums, zig-zag mixers,
and pan agglomerators. Horizontal ribbon
mixers (Fig. 27.34) are used primarily for dry
mix formulating, where only limited agglom-
eration occurs. They are comprised of a
U-shaped trough and a ribbon or paddle-type
agitator. Liquids are sprayed onto the surface
of the dry material and slowly dispersed into
the mix. Mixer operations can be either batch
or continuous. Vertical mixers are more com-
monly used due to low space requirements
and high efficiency of operations. The vertical
mixer (Fig. 27.35) utilizes high-speed agita-
tion to intimately mix and uniformly blend
liquids and dry raw materials prior to dis-
charge. The contact time is reduced to less
than 5 sees. The rotary drum units generally
contain baffles that roll or lift the product for
uniform dispersion or liquid feeds. Pan and
zig-zag agglomerators are generally used for
limited, specialty product manufacture.
The vertical and the rotary drum agglomer-
ation equipment find most widespread use in Fig. 27 .35. Shugi Flex-o-Matic agglomerator.
the detergent industry because of improved
encapsulation. An excellent review of deter-
agglomeration, increased liquid-feed disper- gent agglomeration is available. 4 8,49
sion levels, and optimized product uniformity.
In addition to agglomeration of detergent and
Liquid Detergent Processing
auto-dish detergents, these units can be used
for hydration of STPP, dry neutralization of Liquid heavy-duty products account for
sulfonic acids, post-addition or raw materials approximately 60 percent of the 2001 U.S.
and fines to spray-dried products, and particle laundry detergent market. 50 The growth of
1138 RIEGEL'S HANDBOOK OF INDUSTRIAL CHEMISTRY
heavy-duty liquids began in 1974, as the
result of the phosphate ban in home laundry.
Unbuilt liquids based on nonionic and
anionic/nonionic surfactant combinations
gradually increased in volume for various
reasons including convenience, solubility, and
improved performance versus non-phosphate
containing powdered detergents. In the
mid-1980s, the introduction of higher-
performance liquids accelerated growth in
this segment, with the market share essen-
tially doubling from 1984 to 1990. 51
Liquid products are approximately
50-60 percent water, with the remainder
being a combination of surfactants, builders,
foam regulators, enzymes and enzyme
stabilizers, hydrotropes, anti-redeposition
polymers, optical brighteners, corrosion
inhibitors, dye, and perfume. Two-in-one for-
mulations also contain antistatic and fabric
softening ingredients. Liquid systems require
careful selection and blending of raw materi-
als to achieve a stable product. Special atten-
tion is necessary for the following items:
I. Viscosity. The product must be pourable
and must retain the same viscosity char-
acteristics from batch to batch. This vari-
able can be controlled by proper solvent
or hydrotrope selection
2. Clear-cloud point. The composition
should have sufficient solubility to prevent
hazing or separation of the product when
subjected to storage in cool temperatures
3. Freeze-thaw stability. The formulation
must be compounded to prevent phase
separation or solidification at freezing
temperatures
Most light-duty liquid (LDL) detergents are
formulated using a combination of LAS and
AES with various amphoteric foam stabilizers
(CAPB, amine oxides, and so on). Heavy-
duty liquid detergents often use a combina-
tion of actives such as LAS, AES, AE, and
AOS. The manufacture of liquid products
requires relatively basic equipment for mixing
the various ingredients. The raw materials are
added batchwise to a large mixing vessel
or proportionated to in-line mixers before
being fed to the filling lines. In 1986, liquid
auto-dish detergents were introduced. These
products were based on thixotropic slurries of
STPP and soda ash. The rheology helped to
solve issues with product dispensing rate and
product physical stability. The slurries were
generally viscous enough to prevent prema-
ture dispensing into the dishwasher prior to
the wash cycle. The thixotropic nature of the
product was achieved using natural clays of
high molecular weight polymers. High-shear
mixing equipment such as homogenizers is
used to manufacture these products in batch
or continuous stirred tank systems.
Detergent Trends
In the United States, liquid detergent sales
continue to grow at the expense of powders.
The trend is largely due to convenience as
cost per load for liquids is significantly higher
than for powders. In the United States, liquid
products are clear and isotropic with vibrant
colors. In Europe, liquid products have a
lower market share and are typically based on
structured surfactant systems with suspended
STPP and/or zeolites. These systems tend to
be opaque products and it remains to be seen
if the U.S. market will accept these products.
The performance of liquid laundry detergent
performance has been increased through the
use of multiple enzyme and ancillary ingredi-
ents. Recently, unit dose laundry tablets and
liquid sachets have been introduced in the
United States, which takes customer conven-
ience to the next step. Presently, the market
share for these products is small and it also
remains to be seen how these products will
fare the U.S. market.
The machines used to wash clothes are also
changing. The DOE has mandated energy
efficiency standards on new washing
machines. In order to meet these efficiency
standards, most manufacturers are offering
horizontal axis washing machines similar
to those that have been available in Europe
for many years. The H-axis machines use
less water and energy than conventional top
loader machines, however, they are currently
more expensive than conventional washing
machines. The new machines generate more
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1139

mechanical actions, which in tum generates
more foam. Detergent manufacturers must
now formulate lower-foam detergents for use
in these machines.
The environmental movement, which began
in Europe, is now beginning to appear in the
United States. The use of nonylphenol
ethoxylates in household products is declin-
ing. To a large extent, the NPEs have been
replaced with alcohol ethoxylates. The use of
surfactants that are environmentally accept-
able continues to grow. Surfactants based on
natural, re-growable raw materials are com-
mercially available. Alkyl polyglycosides
based on sugar and fatty alcohol and methyl
ester sulfonates are examples of naturally
derived surfactants. This trend can be
expected to continue into the next decade.

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